Production of low density rigid shapes



vnvvv Ill-I hlihiluh Lnilillllil United States Patent 3,420,682 PRODUCTION OF LOW DENSITY RIGID SHAPES Jay Don Gensler, San Antonio, Tex., assignor to The Dow Chemical Company, Midland, Mich., a corporation of It is a further object of the present invention to provide a low density, porous, high temperature insulating material fabricated from magnesium oxide-magnesium sulfate or calcium oxide-calcium sulfate compositions and a novel method for fabricating such material.

Delaware 5 These and other objects will become apparent after N0 Drawing- Filed 1953, 330,245 reading the detailed description presented heerinafter. Cl. 106-40 5 Claims In general, the present invention comprises hw Int. Cl. C04b 21/02; C04b 35/04 a h dr te M so or h a This invention relates to rigid, refractory materials and, thereby providing a low density, porous, rigid article which more particularly, is concerned with novel, rigid, porous has excellent insulation properties. refractory structures of alkaline earth metal oxide-alka- In order to form said composition of the instant inli e earth metal sulfate compositions an o a rocess for vention, a wet mass of the hydrated sulfite salt is placed Mme-a1 s in a forming apparatus and eated to a temperature and used herein, refers to magnesium and calcium. The terms 15 for a time so as to substantial y remove all of the water aqueous mass" or wet mass, as used herein, refer to of hydration and some of the S0 present therein. Usually, a mass in a form ranging from a thin paste to a substansaid heating is done at a temperature within the range of i ll damp lid, from abouW C. for a time within the The rigid structured products of the instant invention range of from a out2 to a out 4 hours. may be shaped as bars, rods, sheets, cylinders and the like The concentrated paste-like mass of said alkaline earth and find utility as thermal insulators, panels, firewalls, metal sulfite in water should contain enough water t) electrical insulators and insulation for sandwich type conthoroughly wet the salt but not provide any substantial struction material. flow of fluidity.

The product of this invention will Withstand numerous h mold containing the Slurry Should be calcined temperature eyeliugs g g from room temperature 9 fore the moisture can evaporate at low'temperature. The 1000" C. without rup degrading losing its irlsllla' calcining is performed at least until no more smoke or tion values. In addition, this product can be effectively i ibl vapor i being given off. Longer calcining is not employed as an insulator for me at low temperatures if harmful to h product but is not necessary care is taken to exclude condensation and other sources I a preferred f f this invention, the fi t Step is f Water therefrom 3 to prepare a wet mas of hydrated MgSO (MgSO -6H O).

Insulating products known and used heretofore have this may be done by adding water to previously formed one or more drawbacks including for example, failure at MgSO '6H O. Hydrated MgSO may also be prepared by high temperatures, lack of structural strength, high cost, reacting MgO and S0 in an aqueous media e.g. S0 can complicated fabrication methods and limited utility. To mm to give a illustrate further, such common insulation materials as 5 saturated solution, MgO then is added to the aqueous nesiu ate and ma nesium o e lose solution while the S0 bubbling is continued and the enwater of hydration at high temperatures and thus become tire aqueous mixture is being agitated. As the MgO is powdery, crumbly and suffer a reduction in physical added, it dissolves and hydrated MgSO; immediately strength in use. The magnesium-based insulating and reforms. fraetory Preduets employing asbestos degrade when used 40 In general, the preparation of MgSO is preferably done at high temperatures and Usually aVe lime no Physical at room temperature. Higher temperatures can result in strength which contributes to the structural strength of a f ti f detrimental amounts of so W811, enclosure other application Where y be The hydrated MgSO so formed is then removed from p y The fibrous inorganic insulating materials, -g" the mother liquor, and while still in a wet condition,- i.e., a E5 2 2 a g and Similar meterials have no paste-like mass and not in a powdery condition is packed a 5 rerlg and Cannot be effectlvely employed i an into a mold. Usually said paste-like mass is comprised of sulation material in sandwich type panels wherein a por-' f about 75 to 90 percent MgSO3.6H2O The 5.0411165 tion of the structural strength is dependent on the insulamold is placed in a furnace and heated to temperatures in mm materiala range from about 400 to 1000 C. and for a time in a Accordingly, it iS an object Of the present invention it) range from about 2 to 4 hours in order to drive ofi all Provide a novel refractory Composition and a method of the water of hydration along with the excess S0 (i.e., so making the same. a that no more visible vapors are seen). The so-filled mold It is also Q j of the P f invention to PY is allowed to cool (e.g., air cooled). The now-formed a novel composit on of matter which can be fabricated r MgO MgSO4 product is removed from the mold and is any i deslrefj Sham and Whlch finds ready use as seen to be a rigid, porous structure which is not powdery Insulating matenai bothat-lqw tpmperqiines and at or crumbly. The voids in the structure are substantially high temperatures while maintaining its stabi ity, strength uniform in size and distribution. and flame erosion resistance and which has dimensional The r f t d t d f th b stability over a wide temperature range. e me my pro S ma 6 tom e a ove process Another object of the present invention is to provide contam from about 10 to Welght percent a novel composition of matter and a process for utilizing from about 60 to about 90 Percent Mgso4 an the same, said composition of matter offering good strucfrom about 9 to about 0 Weight P e Mg 3- tural strength upon fabrication into rigid, porous shape fOHQWmg examples are merely lnusirailve f h and thus being capable of use in sandwich-type insulating invention disclosed herein and are not intended to limit it construction. thereto.

3 EXAMPLE 1 ln order to show the general characteristics of the composition of matter disclosed herein, the following procedure was carried out:

A wet mass of hydrated MgSO was prepared by bubbling S into 24 liters of water at room temperature until excess S0 was seen escaping from the S0 saturated water. Then, as the S0 bubbling was continued and the aqueous mixture was agitated, MgO was added until a total of about 800 grams was introduced. As the MgO was added, it dissolved with almost instantaneous formation of hydrated MgSO crystals.

The hydrated MgSO crystals were removed from the mother liquor, with retention of sutficient excess water such that the hydrated MgSO was wet but not dripping wet.

710.5 grams of the wet hydrated MgSO was packed into an aluminum foil-lined mold with dimensions of inches by 2 1/ inches by 1 ,5 inches. The so-filled mold was placed in a furnace and was heated for 30 minutes at 275 C., 30 minutes at 400 C. and 2 hours at 575 C. until no more white vapors (S0 were observed.

The specimen was removed from the mold, allowed to cool and the aluminum foil was removed. A bar weighing about 241.4 grams and measuring almost 5 /8 inches by 2 inches by 1 5 inches was produced. The density of the fabricated product was 27.5 unds per cubic foot. The volume 5mm percent. This bar had a rigid, porous structure and was not powdery or crumbly. The voids in the structure were substantially uniform in size and distribution.

In a second run, a wet mass of hydrated MgSO was heated only at 575 C. for 2 hours. The density of the product from this run was found to be 26 pounds per cubic foot and the volume shrinkage was less than two percent.

The compression strength of this material was measured by the following test:

A 3 inch by 1 inch by /2 inch specimen was sawed from the bar and force was applied parallel to the 3 inch axis by using ,a Tinius-Olsen universal testing machine. The machine applied force at a linear loading rate of 0.1 inch per minutes to the point of failure. The compressive strength was thus found to be 274 pounds per square inch.

In a third run, a specimen prepared according to this same process was calcinated for 2 hours at 575 C. Chemical analysis of the final product gave the following data: MgO=20.5 percent, MgSO =79.5 percent,

MgSO =2.0 percent. (The total of 102 percent product indicates that the analytical procedure was not precise.)

In still another run, a similarly prepared specimen was calcinated an additional 4 hours at 800 to 1000" C. and the data obtained on chemical analysis of the final product were the following; Mg0=30.3 percent, MgSO =69.3 percent, MgSO =O.4 percent.

EXAMPLE 2 In order to show the insulation properties of the composition of matter of this invention, the following pro cedure was carried out:

A flame erosion heat conductance test was used on various specimens of commercialy available refractories (controls) and products of the present invention. This test consisted of placing the nozzle of a propane torch two inches away from the specimen to be tested. When the torch was lit, the tip of the flame met the center of the surface of the specimen. Each specimen was inch thick and at least 1 /2 inches wide. A thermocouple was placed in the center of and against the back surface of the specimen to measure the amount of heat passing through. The propane torch caused each specimen tested to become white hot at a temperature of about. 1100 C. Each test specimen was heated to a temperature of ap- 4 proximately 1100 C. The specimens tested and the results obtained are as follows.

Controls (1) Fibrous alumina-silica (commercially known as Fiberfrax): This test specimen was not degraded or eroded by the flame, but the thermocouple indicated that the'back surface of the specimen reached 190 C.

(2) MgCO -asbestos insulating material (commercially known as percent magnesia): This test specimen was completely eroded through in about 6 minutes by the propane torch flame, the eroded area having a charred appearance.

Present inventi0n.-A sample of the same type of material in accordance with the instant invention prepared as shown in Example 1: The test specimen was only slightly eroded in 40 minutes of exposure to the flame. The erosion was in the form of a crack. that measured A inch in depth at its greatest point. No charring was apparent. The thermocouple on the back side registered only 110 C. which indicates that the heat transfer through this test specimen was less than that of the commercially available alumina-silica (Fiberfrax).

Similarly, rigid shapes of CaO-CaSO, are made from CaSO /2H O. The CaSO /2H O is prepared by adding CaO to water which has a large amount of (but not saturated with) S0 dissolved therein. The hydrated CaSO so formed is then removed from the mother liquor and while still in a wet condition, i.e., a paste-like mass, is packed into a mold, calcined and cooled in the same manner as for the hydrated MgSO slurry thereby forming a rigid, porous CaO--CaSO refractory.

The CaOCaSO product so formed is comprised of from about 10 to about 40 weight percent CaO, from about 60 to about weight percent CaSO and from about 20 to about 0 weight percent CaSO Various modifications can be made in the method of the present invention without departing from the spirit or scope thereof for it is to be understood that I limit myself only as defined in the appended claims.

What is claimed is:

l. A novel composition of matter which comprises a rigid, porous, calcined mass consisting essentially of from about 10 to about 40 weight percent alkaline earth metal oxide, from about 60 to about 90 weight percent alkaline earth metal sulfate and from about 20 to about 0 weight percent alkaline earth metal sulfite, said alkaline earth metal being a member selected from the group consisting of magnesium and calcium.

2. A novel composition of matter which comprises a rigid, porous, calcined mass consisting essentially of from about 10 to about 40 weight percent MgO, from about 60 to about 90 weight percent MgSO and from about 20 to about 0 weight percent MgSO;,.

3. A novel composition of matter which comprises a rigid, porous, calcined mass consisting essentially of from about 10 to about 40 weight percent CaO, from about 60 to about 90 weight percent CaSO; and from about 20 to about 0 weight percent CaSO 4. A method for producing low density MgO-MgSO rigid shapes from an aqueous mass of hydrated MgSO which comprises:

(1) placing the aqueous mass consisting essentially of MgSO -6H O into a mold; and

(2) heating said aqueous mass of MgSO -6H O to a temperature within the range from about 400 to 1000 C. thereby removing excess moisture and Water of hydration and converting the MgSO -6H O to a rigid, porous mass of MgOMgSO as defined in claim 2.

5. A method for producing low density CaO-CaSO; rigid shapes from an aqueous mass of hydrated CaSO which comprises:

(1) placing the aqueous mass consisting essentially of CaSO /2H O into a mold; and

6 (2) heating said aqueous mass of CaSO /2H O to a OTHER REFERENCES temperature 'Wlthm the range from f to Sillen et al.: Solid-Gas Equilibria of Importance in 1000 thereby removmg excess mosture and Burning Concentrated Calcium or Magnesium Sulfite water of hydration and converting the CaSO /2H O w t or Sv 5k P 1 55 N 16 5 to a rigid, porous mass of CaOCaSO as defined in 5 ga 5 3 (pages 22?:

claim 3.

HELEN M. McCARTHY, Primary Examiner. References Cited UNITED STATES PATENTS US. Cl. X.R.

3,138,472 6/1964 Sommer 10-61 10 l0687, 88, 64, 105, 109, 58; 23--122, 128, 129 

1. A NOVEL COMPOSITION OF MATTER WHICH COMPRISES A RIGID, POROUS, CALCINED MASS CONSISTING ESSENTIALLY OF FROM ABOUT 10 TO ABOUT 40 WEIGHT PERCENT ALKALINE EARTH METAL OXIDE, FROM ABOUT 60 TO ABOUT 90 WEIGHT PERCENT ALKALINE EARTH METAL SULFATE AND FROM ABOUT 20 TO ABOUT 0 WEIGHT PERCENT ALKALINE EARTH METAL SULFITE, SAID ALKALINE EARTH METAL BEING A MEMBER SELECTED FROM THE GROUP CONSISTING OF MAGNESIUM AND CALCIUM. 